Monoazo dyestuffs



nitecl States Patent @l 2,768,159 Y MONOAZQMESIUFFS Werner Bossarld,Riehen nea lia-sel, and Otto Bitterlin, Basel, "Switzerland,ssigniis"'t'`I."R. Geigyx A. G., Basel, Switzerlandgasvi'issjiirmiclaims priority, appunti@ svygznirq october 17, 1952 9 Claims. (ci. gaa-199) The present invention concerns the production of new monoazodvyestutts "lllayingf1 atlixiityito cellulose bers which can bediazotised anti developed o'n'the fibre;v It also concernsthei'proiductioii"off'wliitedischargeable cellulose dyeings 'withwetfastness p'eij'ties' by diazotising tliimonoaiio dyestuis according'itthe invention on the bre and developing with lcouplingA componentscontain- The main applicationfor substantive cellulose dye-`stusLwliiclqt can he diagotisedand"developed with coupling components"containing 'ino"sulphonlic acid groups on the iibre isforcdi'scllaijgiel ir'ticles.A Discharge print- 2,768,159 Patate@ st,-2.315

"ice

a nu AU .7.1M

pound caribe substituted 'as described ab'ove` for th' henzoyl'radical.j f

Diazo components which can be used according to the invention 'canbe"`oBta`ihed from' 5-a`rnino2'hydrcxybcn zene-l-carboxylic acids whichif desired can be subs't'i tuted in the 3p0sition as :dehed by reactingthem with p-nitrohenzoyl chloride or p-nitrophenyl isocyanate, Vreducingthe nitro to'the` amino group, again reacting with p-nitrohenzoylchloride or p-nitrophenyl isocyanate and reducing the nitro group to theamino group. .lf-desired,

X represents hydrogen, h19rinf?, a @ethyl ms??? benzoylamino] 5hydroxynaphthalene 7 sulphonic acid or 2 [4 (3 amino 4 methylbenzoylamino) benzoylamino] 5 hydroxynaphthalene 7- sulphonicacidofthe-'derivatives"thereof containing an azl-ring mentioned abvecabe used as coupling components.

'111e m1102120 dyssiuffs awarding t0 .the Present i11- ventiion aredistinguished from similar previously known dyesttfs 'by'theirexcellent' aflnityfito cellulose and lay the veryA good'wetfastness'of their 'cellulose dyeing's.' VThe 'dyestus with 'carhoylicacid amidelinkages, YVi. e. those in'vvhch tizi), produce particularlypure shades and are, therefore,'to be preferred, Due tothe good fastnesstofligh'ti' aiid theneicell'eiujt we't'fas'tness properties once1lulo`se,'tl:le new monoazo dyestutfs'can be`us'ed as dil rectcellulose dy'stuiswithout any' after Itreatment what- `V ever. However,by dizotising ori the fibre and developing with coupling components notcontaining any sulphonic acid groups are particularly valuable. Thedirect cellulose dyeings are diazotised in the usual way by reactingwith nitrous `acid in a cold mineral acid solution and developing in analkalinesolution. Unsulphonated enolic or phenolic azo components aresuitable as a developer. It is advantageous however, to use naphtholscoupling in the o-position to the hydroxyl group, in particular2-naphthol.

. Ip the form of their alkali salts the new monoazo dyestuifs areyellow-red to brown-red powders according to the composition. Theydissolve in water with a red and in concentrated sulphuric acid with ablue-red colour.

The following examples illustrate the invention without limiting it inany way. Where not otherwise stated, parts are given as parts by weightand the temperatures are in degrees centigrade. The relationship ofparts by weight to parts by volume is as that of kilogrammes to litres.

Example 1 The sodium salt of 39.1 parts of 5-[4'(4"aminoben zoylamino)benzoylamino] 2 hydroxybenzene-l-carboxylic acid, produced from4aminobenzoyl-S-amino-Z- hydroxybenzene-l-carboxylic' acid by condensingwith 4- nitrobenzoyl chloride and reducing with sodium sulphide, issuspended-in 600 parts of water at room temperature. 5.5 parts ofcaustic soda -and 7.6 parts of -sodium nitrite are' added and the wholeis added dropwise to a mixture of 68 parts of concentrated hydrochloricacid and 68 parts of water. On completion of the diazotisation, thediazonium :ompound is coupled at 20-25 with an aqueous solution of 35.8parts of 2(4aminobenzoylami no)5-hydroxynaphthalene7sulphonic acid inthe presenceof parts of sodium bicarbonate. The next day, the monoazodyestu is precipitated by the addition at 70 of 280 parts of ysodiumchloride and 9.6 parts of caustic s'oda. It is ltered oi and dried.The'dyestuif of the formula:

COOH

is a red powder which dissolves in water with a yellowish red and inconcentrated sulphuric acid with a bluered shade. The dyestuff dyescellulose fibres in pure yellowish-red shades and, diazotised on the breand developed with Z-hydroxynaphthalene, produces pure scarlet dyeingswhich have excellent fastness to water and can be discharged pure white.

If in the above example, instead of 35.8 parts of 2(4 aminobenzoylamino)S-hydroxynaphthalene-7-sulphonic acid the number of parts of thecoupling components given in the following table are used, dyestuffs areob- Example 2 The sodium salt of 40.5 parts of 5-[4(3-methyl4aminobenzoylamino)-benzoylaminol 2-hydroxybenzenel-carboxylic acid issuspended at 20 in 600 parts of water and 5.5 parts of caustic soda and,after the addition of 7.6 parts of sodium nitrite, the whole is added to68 parts of hydrochloric acid 30% and 68 parts of water. The diazoniumcompound is stirred for some hours at 20 and coupled with an aqueoussolution of 35.8 parts of 2-(4aminobenzoy1amino)-S-hydroxynaphthalene 7sulphonic acid and l5 parts of sodium bicarbonate in 720 parts of water.After a few hours, the monoazo dyestuff of the formula:

NH-COGNH,

C O O H Hg H tained with the following properties:

can be precipitated at with 280 parts of sodium chloride and 9.6 partsof caustic soda. The filtered and dried dyestuff is a red powder whichdissolves in water with a yellowish-red and in concentrated sulphuricacid with a blue-red colour. Cellulose fibres are dyed in yellowish-redshades. Ifv the dyestuff is diazotised on the fibre and coupled withA24hydroxynaphthalene, pure scarlet dyeings are obtained which haveexcellent water fastness ahd'which can be discharged pure white.

If in the Aabove example, instead of 40.5 parts of 5-[4f-(3@methyl-4"-aminobenzoylamino) benzoylamino] 2-hydroxybenzene-l-carboxylic acid, the number of parts by wcigiihof anamino. oipound given the ,following carbonate. n completion of thecoupling, the monoazo dyestuif of the formula:

table aire used forv the diazotisation, dyestutfs'withthe I HOaSHoQ-NH-oo-Nn-ONH-COO-N=N oon 1 Y o following properties are obtained?Examplel 3 After adding 5.5 parts of caustic soda and 7.6 parts ofsodium nitrite to the sodium salt of 40.6 parts of 4(4"aminobenzoylamino) 3-carboxy-4-hydroxydiphenyl urea in 600 Vparts ofwater, the suspension-is added dropwise at 20 to 68 parts ofhydrochloric acid" 30% and 68 parts ofl water. The diazonium compoundwhich is obtained after some hours is coupld'at' 0-5 with 35.8 parts of2 (4'aminobenzoylamino)--hydroxynaphthalene-7-sul- Phonic acid in thepresence of 15 parts of sodium bi- The goods are then rinsed in cold'Wirstl we clair-rir is I y ria represents one of the numerals and 1,andZ repre--d l. 'A monoazo dyestuff which corresponds to theV 3`. Aineficaz@ dyestuff which corresponds.V to tlre wherein X represents amember selected from the group formula consisting of H, Cl, CH3, OCHsand SOaH, Y represents HOOG Y wherein X represents a member selectedfrom the group 5 consisting of H, c1, CH3, oem andvsosrfl, Y represents*a member selected from" the-groupconsiatng of H vand a member selectedfrom the group consisting of H and CHa, eeqhoinr, ng andns representsone of the numerals 0 'an'd '1,"A"repres"ents at radical selected fromlthe group consisting ofl CH3, A representsia radical'selcte fromthegroup wnsisting'of -U ""f" Y H038 -NH-C0- 2O HOIS HOgS and

and

HOzS -S HOIS H f t and Z represents a member selected from the groupcon- 0H ssting of H, Cl and CH3. ns represents one of the numerals Q and1, and Z repre- 2; A monozo' dyestufl which corresponds to the sents amember selected from the g'roupconsisting oi H, formula ctandcHs. 1 l fHoot:

Y Y i i. Y t Y n. X Y Y Y Z wherein X represents a memberselected fromthe group 4. A monoazo dyelstuflf which corresponds to the @QnsistingotIL Cl., CH3, @CH3V a'd'SOH, Y tepfeents formula HO NH-C O-NH- NH-C O YY" z A. a member selected from the group consisting of H and whereinrepresents a member selected from the group CH3, A represents a radicalselected from the group conconsistingof H', Cl', CH3', CCH; and' SOsH, Yrepresents sisting of a vmember selected from thevgroupiconsisting of Hand4v CH3 A re resents'a'rdical'selected from the rou con- Ho,s NH-Co-Sistiligof p ,I ,t p

H HVOVIS :C- i.

HOzS NH and and

HOsS S n3 represents one of the numerals 0 and 1, and Z repre- 5. Amonoazo dyestu having the formula:

NH--CO H 6. A monoazo dyestui having the formula:

III-[05S NB-C OQNH; HoQNH-oo-O-NH-C oN=N H.

O O H H 7. A monoazo dyestuf having the formula:

Hogs HoQNH-c o-O-NH-C 0QN=N oon n, n

8. A monoazo dyestuff having the formula:

9. A monoazo dyestuff having the formula:

References Cited in the le of this patent UNITED STATES PATENTS NH-C 0NH-O O NH,

N11-o o-O-NH,

2,232,870 Roos Feb. 25, 1941 2,263,559 Krst Nov. 25, 1941 2,381,599Krebser et al Aug. 7, 1945 2,418,624 Chechak et al. Apr. 8, 1947

1. A MONOAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA WHEREIN XREPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF H, CL, CH3,OCH3 AND SO3H, Y REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTINGOF H AND CH3, EACH OF M, N2 AND N3 REPRESENTS ONE OF THE NUMERALS 0 AND1, A REPRESENTS A RADICAL SELECTED FROM THE GROUP CONSISTING OF